Polyamide fibers dyed with thiadiazolyl azo compounds

ABSTRACT

POLYAMIDE FIBERS ARE DYED BRIGHT, FAST RED TO PINK SHADES WITH A COMPOUND HAVING THE FORMULA   2-((4-(R2-N(-(CH2)N-X)-),3-R1,6-CH3-PHENYL)-N=N-),5-   (R-Y-)-1,3,4-THIADIAZOLE   IN WHICH R IS AN ALKYL, ALLYL, ARYL, OR CYCLOHEXYL RADICAL, Y IS -O- OR -S-, R1 AND R2 EACH IS HYCROGEN OR ALKYL, N IS 2 OR 3, AND X IS PYRROLIDINONO, ACRYLAMIDE, CARBOMYL OR ACYLOXY.

nited States Patent 3,738,802 POLYAMIDE FIBERS DYED WITH THIADIAZOLYLAZO COMPOUNDS Max A. Weaver and David J. Wallace, Kingsport, Tenn,assignors to Eastman Kodak Company, Rochester, N.Y. No Drawing. Originalapplication June 16, 1969, Ser. No. 833,745, now Patent No. 3,657,187.Divided and this application Jan. 6, 1972, Ser. No. 215,915

Int. C1. C09!) 29/36 US. Cl. 8-41 B 9 Claims ABSTRACT OF THE DISCLGSUREPolyamide fibers are dyed bright, fast red to pink shades with acompound having the formula in which R is an alkyl, allyl, aryl, orcyclohexyl radical; Y is O- or S-; R and R each is hydrogen or alkyl; nis 2 or 3; and X is pyrrolidinono, acylamide, carbamoyl or acyloxy.

This is a divisional application of our application Ser. No. 833,745filed June 16, 1969, now US. Pat. 3,657,187 for ThiadiazolylazoCompounds and Polyamide Textile Materials Dyed Therewith.

This invention relates to certain novel, water-insoluble azo compounds,and more particularly, to novel 1,3,4- thiadiazolylazo dyes and topolyamide textile materials dyed therewith.

The novel compounds of the invention have the formula NN IR z) n CH3wherein R is an alkyl, allyl, cycloalkyl, or aryl radical;

R is hydrogen or lower alkyl;

R is hydrogen or lower alkyl;

n is 2 or 3; and

X is hydrogen, pyrrolidinono, lower alkanoylamido, loweralkoxycarbonylamine, aroylamido, carbamoyl, lower alkanoyloxy,2,2,4-tri-lower-alkyl-3-oxo-valeryloxy, or aroyloxy.

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valuable for the dyeing of polyamide fibers than are those disclosed inFrench Patent 1,503,249 which relates primarily to azo compoundsparticularly suitable for dyeing cellulose acetate and polyester textilematerials.

The lower alkyl radicals represented by R can be substituted orunsubstituted, branchedor straight-chain alkyl. Methyl, ethyl, propyl,isopropyl, butyl, isobutyl, etc. are typical unsubstituted alkyl groupsrepresented by R. Typical groups which can be present on alkyl radical Rinclude hydroxy, e.g. 2-hydroxyethyl, 3-hydroxypropyl; halogen, e.g.2-chloroethyl, 3-bromopropyl; lower alkoxycarbonyl, e.g.2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl; lower alkanoyloxy, e.g.2 acetoxyethyl; lower alkoxy, e.g. Z-methoxyethyl; lower alkanoyl, e.g.2-acetylethyl; aroyl, e.g. benzoylmethyl; cyano, e.g. 2-cyanoethyl;carbamoyl, e.g. 2-carbamoylethyl; dicarboximido, e.g.3-succinimidopropyl; etc. As used herein to describe an alkylmoiety-containing group, lower designates a carbon content of up toabout 4 carbon atoms. The alkyl radical represented by R can also besubstituted with cycloalkyl,.e.g. cyclopentyl, cyclohexyl, cycloheptyl,and lower alkyl-substituted derivatives thereof, and with aryl, e.g.phenyl and phenyl substituted with lower alkyl, lower alkoxy, orhalogen. Cyclohexylmethyl, 2-cyclopentylethyl, 4 ethylcyclohexylmethyl,4-methoxycyclohexylmethyl, 2- (3-chlorohexyl)ethyl, benzyl,p-methylbenzyl, 2-p-ethoxyphenylethyl, 4-chlorobenzyl, 2-phenylethyl,etc. are illustrative of the cycloalkylalkyl and arylalkyl groups whichR can represent. Examples of the cycloalkyl and aryl groups which R canrepresent are set forth hereinabove.

Methyl, ethyl, propyl, and butyl are representative of the lower alkylgroups which R and R can represent. Acetamido, propionamido, butyramido,acetoxy, propionoxy and butyroxy are typical alkanoylamido andalkanoyloxy group represented by X. Examples of the valeryloxy groupsrepresented by X include 2,2,4-trimethyl-3- oxovaleryloxy and2,2,4-triethyl-3-oxovaleryloxy. Examples of the alkoxycarbonylaminogroups represented by X include methoxycarbonylamino,ethoxycarbonylamino, propoxycarbonylamino, and butoxycarbonylamino. Thearyl moiety of the aroylamido and the aroyloxy groups represented by Xcan by phenyl or phenyl substituted, for example, with lower alkyl,lower alkoxy or halogen. 2- acetamidoethyl, 3 propionamidopropyl,Z-butyroxyethyl, 3 acetoxypropyl, 2 (2,2,4-trimethyl-3-oxovaleryloxy)ethyl, 2 (2 pyrrolidinono)ethyl, Z-carbamoylethyl, 2- benzamidoethyl,3-p-toloylamidopropyl, Z-p-chlorobenzoylethyl, 2-benzoyloxyethyl, etc.are specific examples of the groups which -(CH X can represent.

Unusually bright and light-fast shades of varying depths are produced onpolyamide, e.g. nylon 66 and nylon 6, fibers, yarns and fabrics by thenovel compounds of Formula I wherein R is methyl or ethyl, Y is -S, R ishydrogen or methyl, R is hydrogen or lower alkyl, one of R and R ishydrogen, n is 2 or 3, and X is hydrogen, carbamoyl, loweralkanoylamido, lower alkanoyloxy, 2,2,4 trimethyl-3-oxovalery1oxy,2,2,4-triethyl-3-oxovaleryloxy, or lower alkoxycarbonylamino.

The novel azo compounds are prepared according to known procedures bydiazotizing a compound having the formula (II) NN and coupling thediazonium salt with a coupler having the formula 4 EXAMPLE 1 Sodiumnitrite (0.72 g.) is added portionwise to 5.0 ml. of cone. H 50 withstirring. The solution is cooled R: and 10 ml. of 1:5 acid (1 partpropionic acid:5 parts 5 acetic acid) is added below 15 C. Aftercooling, 2-amino- 5-(ethylthio)-l,3,4-thiadiazole (1.61 g.) is added,foll CHm-X lowed by ml. 1:5 acid, all below 5 C. The diazotiza- CH3 tionreaction is stirred and kept at 05 C. for 2 hr. and

is then added to a chilled solution of N-(Z-carbamoyl- 10ethyl)-N-ethyl-m-toluidine (2.06 g.) dissolved in 40 ml. of 1:5 acid.The mixture is kept cold while ammonium The couplers of Formula III areobtamed by puPllshefl acetate is added until the mixture is neutral toCongo Red Procedures- The compounds Formula H f Y test paper. Afterallowing to couple for 1 hr., the product Sulfur can be P FP accorflmgto {Onvennonal Proce' is precipitated by the addition of Water,collected by filtradllfes y alkylatlng afylatlng P -Ll 15 tion, dried,and recrystallized from methanol. The prod- 4-thiadiaz0le (Ber. 28, 946,British Patent 726,045). The 4-(5 1h 1thi0-1,3,4-thiadiazol-2-ylazo) N(2-caralkylation and arylation reactions, employing alkylhalbamoylethyl)-N-ethyl-m-toluidine, melts at 180182 C., ides, alkylsulfates, alkyl phosphates, aryl bromides or produces bright pink shadesof excellent light-fastness and iodides, etc. can be carried out atelevated temperatures build-11p on nylon t-ricot and nylon carpetmaterial. in a variety of solvents, e.g. water, alkanols,dimethylfiomllounds dlsclosed 1n the table p pf f formamide, in thepresence of a base such as potassium by dlaZOtlZmg Q- 11101 F'P Pamlnothladl carbonate or sodium acetate. The compounds of Formul $5 andco tphng tllle dlazonum salt 31th 0.01d moldof II wherein Y is oxygencan be synthesized by published applopna e coup er accol mg to t e proceme h I Ch S 1967 2700 2704) scribed in Example 1. The azo compounds setforth 1n tee mques T the examples of the table impart bright red to pinkshades The Preparanon of the novel compounds of the mvcn' havingexcellent fastness to light on polyamide fibers. The tion is furtherillustrated by the following examples. compounds disclosed in the tableconform to Formula I.

TABLE Ex. No. R Y R1 R2 n X 2 CHu(cyclohexyl) S H -C H 2 --NHCOCH3 C H sH -C2H 2 -OOCC(CHa)2COCH(CH CH2=CHCHP s H -C H 2 -NHCOCH CHs- S 1'1 C2H52 -O0CCOH5 C2 s' s H CzH5 2 -0OCCH CHs- S H -oH5 3-NHOOC(CH3)2COCH(CH3)2 C2 s S H --CH5 2 NHCOCH3 02115- O H C2H5 3-NHCOCH3 CzH5 0 H CzHs 3 -NHCOOI-I3 (M15- s H C2H5 3 -NHCOCH C2H5- S -CHCH3 2 -NHCOCH3 CzHs- S H CH3 3 NHCOCH3 C2H5- S H CH2CH(CH3)2 3 -NHCOGH3C2H5' s H CH(OIIs)CHzClI 2 -NHCOCH1 C2 5' S 11 C1I*I5 2 --NHCOCol 5CHBCHKCHQCHis H -C H,, a -NHooCuI, CH3CH(CH3)CHg- 0 II -C2H5 3 NHCOCBH5C5Hs o H C@H5 2 NHCOCH1CH3 -C2 s S H -C2H5 2 NHCOCHCH3 CH3(CH2)3 S H-(CH2)2CH3 2 NHCOCoH4 'OCI-I cHaoHms H (CHz) CH 2 -NHOOC5H4p-CH CH(OH2); s H CzH5 2 NHCOCeH4-p-C1 0H3 CH2)3 o H -CzH5 2 NHCOC H4p-C1 (CH32GHCH2- o H C;;H 2 -CONH (GH3)2CHCH2 S H --CzH5 2 CONH3 GHZZCHCHT- S H-CzH5 2 CONH1 CHg -CHCH S H --C2H5 2 NHCOCHZCHZCH3 CHZ=OHCH2 s H CgH5 3-NHCOCH; CH2=CHCHzo H 02H5 3 NHCOCH CsHn O H -CzH5 2 -CONH2 C5Hu- S HCZH5 Z CONH3 l CzH s H -o2H5 2 Alooomomon, 0H;- s H -CZH5 2 NHCOGH3 CHa-S H --C2H5 2 -CONH3 CH3- S H C H5 2 o0ooH 37 C2H5- S H -C2H5 2 -CONH238.. CzHs- S H -C:H5 2 NHCO0C2H5 39.. H0OH20H1- s H CZH5 2 -NHCOCH3 40..HOCHzCHz- S H C2H5 2 -CONH2 41.. HOCHzCH: o H -C2H5 2 CONH 42..CICH2CH2- S H -C2H5 2 CONH2 43.. CHQOOCCHZCHP s H CH 2 CONHZ 44"CHaCOOCHaCHr S H C2H5 2 CONH2 45.- CHSCOOOH2CH2 o H -C2Hr 2 CONH2 4s.001150112- 0 H C2H5 2 NHCOCH3 47-. CoHaCHz- S H 'CzHs 3 --NHCOCH2 48.-CHaO-p-C5H4CH2- s H -C2H, 2 NHCOOC1H 49-. CHap-CH4CH S H CzH 2 NHCOOCH250.- 4-CH3cy 1 exy1OHis H -C1H 2 OOCCH(CH;) 51.- 4-CH -cyclohcxy1CH s H-C2H 2 -NHCOCH: 52 CHaCOOHzOHrs H -o2H 2 NHCOCH: 53 CH3COCH2CH2- s H--C;H 2 CONH1 54 OH3COGH2CH2 0 H -oiH6 2 -C0NH2 55 CeHsCH2CH2- O H C2H52 CONH1 56 CoHsCHzCHzs H -O H5 2 -CONH 57 CGHaCHzCHrs H -o2H 3 -NHCOC6H55s otHbcooH s H -CZII5 3 -NHCOC(CH3)2COCH(CH3)2 59.. NCCH2CH2 s H CH 2-OOCCuH4p-CH 60 HzNCOCHaCHr S H -C:H5 2 -NHCOCH3 l l 61COCHzCHaCONHGHzCHr S -C2H5 2 NHCOCH3 a 5 S CH3 H 2 NHCOCH3 6115- 0 CH3 H2 -NHCOCH3 CHs-p-CeHa- S CH3 H 3 NHCOCH3 The novel azo compounds can beapplied to polyamide textile materials according to known dispersedyeing techniques. Various dispersing and wetting agents can R is loweralkyl; lower alkyl substituted with hydroxy, halogen, lower alkoxy,succinimido, cyclohexyl, lower alkylcyclohexyl, or aryl; allyl;cyclohexyl; cyclohexyl substituted with lower alkyl; or aryl;

R and R each is hydrogen or lower alkyl, one of R and R being hydrogen;

n is 2 or 3; and

X is pyrrolidinono, lower alkanoylamido, lower alkoxycarbonylamino,aroylamido, carbamoyl, lower alkanoyloxy, 2,2,4-tri-lower-alkyl 3oxovaleryloxy, or aroyloxy;

in which each aryl is phenyl or phenyl substituted with lower alkyl,lower alkoxy or halogen.

2. A fiber according to claim 1 wherein the polyamide ispoly(hexamethylene adipamide) or poly(caprolactam).

3. A fiber according to claim 2 wherein the fiber is dyed with acompound having the formula be employed in the dispersion of the finelydivided dye I l R compound in an essentially aqueous dyebath. Proceduresi l by which the compounds of the invention can be applied S topolyamide textile materials are described in US. E CHQFX Pats. 3,100,134and 3,320,021. The following example illustrates a method for applyingthe novel compounds wherein R is methyl or ethyl; Y is S; R is hydrogento polyamide fibers. 10 or methyl; R is hydrogen or lower alkyl; one ofR and R is hydrogen; n is 2; and X is carbamoyl, lower alkano- EXAMPLE64 ylamido, lower alkanoyloxy, 2,2,4-trimethyl-3-oxovaler- The azocompound (50.0 mg.) of Example 6 is disyloxy, 2,2,4-triethylvaleryloxyor lower alkoxycarbonylpersed in 5 cc. of Z-methoxyethanol. A smallamount amino. (3-5 cc.) of a 3% sodium lignin sulfonate solution is 5 4.A fiber according to claim 2 wherein the fiber is added, with stirring,and then the volume of the bath is dyed with a compound having theformula brought to 150 cc. with water. A 5 g. textile fabric made ofnylon 66 fibers is placed in the bath which is then N C slowly broughtto the boil. The dyeing is carried out at l l 2 the boil for one hourwith occasional stirring. The dyed CIHfiS S fabric is then removed fromthe dyebath, rinsed with CH CH NHOOCH water, and dried in an oven at 250F. The fabric is dyed CH3 z gg fizg f gi zi zg g l z i fi igg gfg gfgg5. A fiber according to claim 2 wherein the fiber is described in theTechnical Manual of the American dyed with acompound havmg the formulaAssociation of Textile Chemists and Colorists, 1968 edition. I

The polyamide materials which can be dyed with the (1 1-1 5 s N: novelazo compounds are well-known and include nylon 66 (polyhexamethyleneadipamide) manufactured by the 0 11 GH2OHZNHCOOC2H polymerization ofadipic acid and hexamethylenediamine, nylon 6 (polycaprolactam) preparedfrom epsilon-amino- A fiber aCCOfding t0 Plaim 2 wherein the fiber iscaproic acid lactam (caprolactam), and nylon 8. A dey with a compoundhill/111g the formula tailed description of the synthetic polyamidematerials which are dyed bright, fast shades by the compounds of N N theinvention is set forth in US Pat. 3,100,134. JL L The invention has beendescribed in detail with par- 021158 S N=N ticular reference topreferred embodiments thereof, but I z z00C0H3 it will be understoodthat variations and modifications 4o 3 can effected Wlthm the $13111tand Scope of the 7. A fiber according to claim 2 wherein the fiber isdyed ventlon' with a compound having the formula We clalmz 1. A fiberhaving a basis of a linear synthetic poly- NN amide dyed with a compoundhaving the formula l L 1 6 s 3' I 1 R= CH omorrmnooon; R-Y N=N N 3 s(CH2)n-'X 8. A fiber according to claim 2 wherein the fiber is 5 dyedwith a compound having the formula NN C H J- 2 a (E ms N: -N

Ha CHzCHgOOOC(CH3)2COCH(CH3)3 wherein 9. A fiber according to claim 2wherein the fiber is dyed with a compound having the formula ReferencesCited UNITED STATES PATENTS CH CH CONHH GEORGE F. LESMES, PrimaryExaminer P. C. IVES, Assistant Examiner

